Sulfurous phosphoric and phosphonic esters

ABSTRACT

New and valuable sulfurous phosphoric ester derivatives and a process for controlling pests with these compounds.

United States Patent [1 1 Beutel et al.

[ SULFUROUS PHOSPHORIC AND PHOSPHONIC ESTERS [75] Inventors: Peter Beutel, Mannheim; Heinrich Adolphi, Lirnburgerhof; Karl Kiehs, Lampertheirn, all of Germany [731 Assignee: BASF Aktiengesellschaft,

Ludwigshafen (Rhine), Germany 221 Filed: 0c1.10,1973 [2i] Appl. No: 405,157

[30] Foreign Application Priority Data Oct. 12, 1972 Germany 2249939 1 July 22, 1975 Primary ExaminerAnton H. Sutto Attorney. Agent, or Firm-Johnston, Keil, Thompson & Shurtleff [57] ABSTRACT New and valuable sulfurous phosphoric ester derivatives and a process for controlling pests with these compounds.

2 Claims, No Drawings 1 SULFUROUS PHOSPHORIC AND PHOSPHONIC ESTERS The present invention relates to new sulfurous phosphoric and phosphonic esters and their use as pesticides.

it is known to use phosphoric esters and methyl carbamates as insecticides. However. pests which have developed a resistance to these active ingredients are on the increase.

We have now found that phosphoric ester derivatives of the formula where R denotes methyl or ethyl, R denotes methyl, ethyl, phenyl, methoxy or ethoxy, R denotes alkyl of a maximum of 3 carbon atoms (methyl, ethyl, n-propyl, isopropyl), R denotes hydrogen. alkyl of a maximum of 3 carbon atoms (methyl, ethyl, n-propyl, isopropyl) or phenyl, or R and R together with the nitrogen atom whose substituents they are denote a pyrrolidine, piperidine, morpholine, piperazine or N-alkyl piperazine ring, R denotes alltyl of a maximum of 3 carbon atoms (methyl, ethyl, n-propyl, isopropyl), R denotes methyl. ethyl or phenyl and X denotes oxygen or sulfur, have excellent acaricidal and insecticidal properties. They have a very good action not only on biting and sucking insects, but also on mites. Phytotoxicity is low. The action sets in rapidly and lasts for a long time. For this reason the compounds of the invention may be successfully used in the plant protection sector for combatting injurious sucking and biting insects and Diptera, and for eombatting Acarina in the plant protection and veterinary sectors. Of special importance in this connection is the excellent action of the compounds on strains of mites which are resistant to phosphoric esters.

The main members of the group of sucking insects are aphids such as the green peach aphid (Myzus per- .rlcae) and the bean aphid (Doralis fabae); scales. such as Aspldiotus hederea, Lecam'um hesperidum, Pseudococcus marinmus; Thysanoptera, such as Hercinorhrips femurall's; and bugs. such as Piesma quadrata and the bed bug (Clmex Iecmlarius).

The main members of the group of biting insects are caterpillars, such as Plutella maculi'pennis and Lymantria dispnr; beetles. such as the granary weevil (Sitaphllus granarius), Colorado potato beetle (Leptlnararsa decemllneata), and also types living in the soil, e.g., wireworms (Agrlotes sp.) and cockchat'er (Melalam/m melalsmha); bugs, such as the eroton bug (Blartela germanlca); Ortheptera, such as the house-cricket (Gryllus domes-liens); termites, such as Reticulitermes; and Hymenoptera, such as ants.

The Diptera include in particular the flies, e.g.. fruit fly (Drosophila melanoguster); Mediterranean fruit fly (C eralitis capilam); housefly (Musca domestica); gnuts such as the yellow fever mosquito (Aedes aegypri) and Calm pipilus; blue-bottles, such as Luriha .ltl'iCdId, and blowflies (Chrysomya chloropyga 0f. the mites, the following are of particular importance: Tetranychidae, such as the red spider mite (Terranychus urticae) and Pararerranydtus pilusus; gall mites. such as the currant mite (Erioplrves rihis) and Tarsonemidae. such as Tarsonemus pal'h'dus.

Application of the compounds is by conventional methods, e.g.. spraying, atomizing. fuming. broadcasting, etc.

The new active ingredients may be prepared from the appropriately substituted chloroacetic amidines in accordance with the following equation:

where R to R and X have the above meanings, hal denotes chloro, bromo or iodo and B denotes any organic or inorganic cation (e.g. Na*, K. NHQ, (C H ),,NH,,*, s s)s Examples of suitable solvents for the reaction are cyclic or acyclic ethers such as dioxane. tetrahydrofuran. ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone and methyl ethyl ketone; hydrocarbons, e.g. benzene, toluene, xylene; and chlorinated hydrocarbons, e.g. chloroform. carbon tetrachloride. chlorobenzene. The reaction may also be carried out in water or mixtures of water and any of the abovementioned water-miscible or waterimmiscible solvents.

The reaction may be carried out at from 0 to lC. preferably to I00C. The haloacetamidines substituted as mentioned above are prepared for instance by the following reaction:

HCl

(cf. Angew. Chem, 80, 179, 1968). The radicals R to R have the abovementioned meanings.

EXAMPLE I a. Preparation of N.N-dimethyl-N'-dimethylaminosulfonyl chloroacetamidine The agents according to the invention may be used as solutions. emulsions. suspensions or dusts. The form of application depends entirely on the purpose for which the agents are being used. in any case it should At 35 to 40C and over a period of It) minutes l l7 5 ensure a line distribution of the active ingredient, parts (by weight) ofchlorosulfonyl isocyanate is added For the preparation of solutions to be sprayed direct, to lOl parts ofN.N-dimethylchloroacetamide and l50 the solution in water is suitable. However. hydrocarparts of carbon tetrachloride. The mixture is then bons having boiling points higher than l50C, e.g. tetstirred for a further 90 minutes at 40C until complerahydronaphthalene or alkylated naphthalenes, or ortion of the reaction. A solution of 75 parts of dimethyll ganic liquids having boiling points higher than l50C amine in l50 parts of dioxane is then dripped in over and having one or more than one functional group. e.g. a period of 30 minutes at 0 to C. After all has been he keto group, th her gr p, he t r group r th added the mixture is stirred overnight at room tempera mi e g p. i gr p r hese gr up being attached t as substituent(s) to a hydrocarbon chain or being a The contents of the flask are filtered and the filtrate l5 compone"t of a heterocydic Ting, y also be used as is concentrated. The residue is dissolved in chloroform, p y hquids washed twice with water, dried over sodium sulfate and Aq f rm l ion may be prepared from emulconcentrated, sion concentrates, pastes or wettable powders by add- Yield: 75 to 85%; mp: 76 to 78C. ing water. To prepare emulsions the ingredients as such bi Pre ar i f or dissolved in a solvent may be homogenized in water S-(0.0-diethylthiophosphoryl)-N,N-dimeth or organic solvents by means of wetting or dispersing N'-dimethylaminosulfonylthiolglycolic amidi agents, e.g., polyethylene oxide adducts. Concentrates At to C and over a e i d f 1 h 1 024 which are suitable for dilution with water may be preparts of N,N-dimethyl-N-dimethylaminosulfonyl chlopared from acfive ingrediemi emulsifiying dispersiilg roacctamidine is added in portions to a solution of 955 25 agent and Possible soil/enparts of ammonium-0.0-diethyldiethiophos hate in Dusts or granules may be prepared by mixing or 2,000 parts of dioxtme and 400 parts f w t Th i grinding the active ingredients with a solid carrier, e.g., ture is then stirred for 4 hours at C. The contents of g talc. lay Of f rtilizerthe flask are cooled and diluted with about 1,000 parts of water. The product is suction filtered and washed EXAMPLE 2 two to four times with water to remove the inorganic impurities. parts by weight of the compound of Example I 15 Yield: l00%; m.p. 46 to 48C. mixed with l0 parts by weight of N-methyl-a- The following compounds may be prepared l pyrrolidone. Amixture is obtained which is suitable for gously: application in the form of very fine drops.

s EXAMPLE 3 20 parts by weight of the compound of Example 1 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to l mole of oleic acid-N- monoethanolamide. 5 parts by weight of the calcium salt of dodecylbenzenesulfonic aditL'and 5 parts by weight of the adduct of 40 moles ofethylene oxide to l mole of castor oil. By pouring the sol'titioninto l00.000 parts by weight of water and uniformly distributing it therein. an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 4 20 parts by weight of the compound of Example l is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of '7 moles of ethylene oxide to 1 mole of isooctylphenol, and I parts by.

weight of the adduct of 40 moles of ethylene oxide to l mole of castor oil. By pouring the solution into 100.000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 5 EXAMPLE 6 20 parts by weight of the compound of Example 1 is well mixed with 3 parts by weight of thezsedium salt of diisobutylnaphthalene-a-sulfonic acid, l7 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor. and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 7 3 parts by weight of the compound of Example 1 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

EXAMPLE 8 30 parts by weight of the compound of Example 1 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

The biological experiments were carried out with the following active ingredients:

For comparison purposes the following prior art compounds were used:

EXAMPLE 9 Action on red spider mite (Tetranychus telarius) Active Aetiw ingredient content in ingreaqueous formulation in wt); Llient no. O.l 0.02 Ulll 0.005

I mortality I: l llliJ I I00 80 I I00 I00 85 3 I00 IOl) 9O 4 IOU IOU HO 6 IOO IOU 8O 7 I00 I00 85 X IOO I00 I00 85 9 IOU lIlO 80 II] IOU 95 I l I00 I00 I00 KO l2 I00 95 I3 I00 I00 I00 80 I4 IOU I00 I00 8O l I00 I00 )0 lo I00 I00 I00 90 IX I00 I00 80 compara tivc 85 0 0 agent I EXAMPLE IO Action on the bean aphid (Aphis fabae) Potted bean plants (Vicia faba) suffering heavy attack from bean aphids (Apliis fabae) are treated as in Example 9 with aqueous emulsions of the active ingredients in a spray chamber.

The action is determined after 48 hours.

EXAMPLE I I Action on caterpillars of the cabbage moth (Plutella mat'ulipennis) Young cabbage leaves are dipped for 5 seconds into aqueous emulsions of the active ingredients. After the leaves have dried they are put in Petri dishes. Caterpil- Iars of the cabbage moth in the 4th larval stage are then placed on the leaves.

The kill rate is determined after 48 hoursv Active Active ingredient content of ingredient emulsion in wt;

no. 0.2 0.1 0.05 0.025 01H 1 mortality (94) I00 I00 I00 I00 30 2 mortality (/4 100 I00 I00 30 3 mortality (71) I00 I00 I00 I00 40 4 mortality (71) 100 I00 20 5 mortality (54) I00 I00 I00 I00 30 I6 mortality (71) I00 I00 I00 I00 )0 l7 mortality lZ) I00 I00 I00 I00 40 Ill mortality (/11 I00 I00 I00 30 comparative agent Ill mortality (1] I00 20 0 We claim:

I. A phosphoric ester of the formula where R denotes methyl or ethyl, R denotes methyl, ethyl, phenyl, methoxy or ethoxy, R denotes alkyl of a maximum of 3 carbon atoms, R denotes hydrogen or alkyl ofa maximum of 3 carbon atoms, R denotes alkyl of a maximum of 3 carbon atoms, R denotes methyl, ethyl or phenyl, and X denotes oxygen or sulfur.

2. S-(0,0-diethylthiophosphoryl)-N,N-dimethyl-N clime'thylaminosulfonylthiolglycolic amidine. 

1. A PHOSPHORIC ESTER OF THE FORMULA R1-O-P(=X)(-R2)-S-CH2-C(=N-SO2-N(-R3)-R4)-N(-R5)-R6 WHERE R1 DONATES METHYL OR ETHYL, R2 DONATES METHYL, ETHYL, PHENYL, METHOXY OR ETHOXY, R3 DONATES ALKYL OR A MAXIMUM OF 3 CARBON ATOMS R4 DONATES HYDROGEN OR ALKYL OF A MAXIMUM OF 3 CARBON ATOMS, R5 DENOTES ALKYL OF A MAXIUM OF 3 CARBON ATOMS, R6 DENOTES METHYL, ETHYL OR PHENYL, AND X DENOTES OXYGEN OR SULFUR.
 2. S-(O,O-diethylthiophosphoryl)-N,N-dimethyl-N'' -dimethylaminosulfonylthiolglycolic amidine. 